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Construction of Supramolecular Complexes via Tandem Claisen Rearrangement and Their Functions

串联克莱森重排超分子配合物的构建及其功能

基本信息

批准号：
19550132
负责人：
HIRATANI Kazuhisa
金额：
$ 2.91万
依托单位：
Utsunomiya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2007
资助国家：
日本
起止时间：
2007 至 2009
项目状态：
已结题

项目摘要

Not only macrocyclic but also noncyclic compounds having plural amide, catechol, and/or phenolic groups were synthesized in good yields via tandem Claisen rearrangement (TCR). Macrocyclic compounds (amidecrownophanes) formed supramolecular complexes with dihydrogen phosphate and fluoride ions exhibiting specific fluorescent emission.Noncyclic and macrocyclic compounds after TCR formed boron complexes by the reaction with sodium borohydride in high yields. These boron complexes were found to emit strong fluorescence in the range of 400 to 500nm. In particular, the fluorescence intensity of the macrocyclic boron complexes drastically increased depending upon the ring size of macrocycles when lithium ion was added to the solution.On the other hand, tripodands having three arms were prepared which can converted into the compounds having plural hydroxyl groups by TCR. They can react with Ti (IV) metal ions to form cryptand-type 1:1 complex. In addition, the cryptand-type metallo-supramolecular complex can include selectively metal ions and ammonium ions into the cavity. Besides, it was also found that the tripodands after TCR can include anion species. Noncyclic compounds having catechol moiety after TCR were prepared. They can make 3:1 complex with Ti (IV) ion. The structuire was successfully cleared by X-ray structural analysis and NMR spectroscopic methods.

通过串联Claisen重排（TCR），不仅可以合成大环化合物，还可以合成具有复数酰胺、儿茶酚和/或酚基的非环化合物。大环化合物与磷酸二氢和氟离子形成超分子配合物，表现出特定的荧光发射。TCR后的非环和大环化合物与硼氢化钠反应生成硼配合物，收率高。发现这些硼配合物在400 ~ 500nm范围内发出强荧光。特别是，当锂离子加入到溶液中时，大环硼配合物的荧光强度急剧增加，这取决于大环的环尺寸。另一方面，制备了具有三臂的三足化合物，经TCR可转化为具有多个羟基的化合物。它们能与Ti （IV）金属离子反应形成隐型1:1配合物。此外，隐型金属-超分子络合物可以选择性地将金属离子和铵离子纳入空腔。此外，还发现TCR后的三足动物可以包含阴离子。制备了经TCR后具有儿茶酚部分的非环化合物。它们能与Ti （IV）离子形成3:1的配合物。通过x射线结构分析和核磁共振波谱分析，成功地确定了该结构。